CN114404658B - Bone cement, preparation method thereof and orthopedic implant material - Google Patents
Bone cement, preparation method thereof and orthopedic implant material Download PDFInfo
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- CN114404658B CN114404658B CN202210155515.3A CN202210155515A CN114404658B CN 114404658 B CN114404658 B CN 114404658B CN 202210155515 A CN202210155515 A CN 202210155515A CN 114404658 B CN114404658 B CN 114404658B
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- 239000002639 bone cement Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 41
- 230000000399 orthopedic effect Effects 0.000 title claims abstract description 16
- 239000007943 implant Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 58
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 50
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 50
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007790 solid phase Substances 0.000 claims abstract description 42
- 239000007791 liquid phase Substances 0.000 claims abstract description 38
- HZILEUCPZSKSTI-UHFFFAOYSA-N CC(C(OC(C1=CC=CO1)[N+]([O-])=O)=O)=C Chemical compound CC(C(OC(C1=CC=CO1)[N+]([O-])=O)=O)=C HZILEUCPZSKSTI-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 nitrofurfuryl alcohol ester Chemical class 0.000 claims abstract description 28
- 239000004568 cement Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 7
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- 239000000316 bone substitute Substances 0.000 description 2
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 description 2
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention discloses bone cement, a preparation method thereof and an orthopedic implant material, and relates to the technical field of medical materials. The bone cement comprises: the solid phase component comprises 80-99% of self-curing calcium phosphate cement and 1-20% of poly (nitro-furfuryl methacrylate); liquid phase component comprising citric acid and Na 2 HPO 4 The mixed aqueous solution of (1). The polymethacrylic acid nitrofurfuryl alcohol ester belongs to a biological base material, has high biological safety, better biological activity and excellent antibacterial property, excellent thermal stability and mechanical property, good bonding property with a calcium phosphate bone bonding material, can effectively reduce tissue thermal injury, has the heat release temperature lower than 60 ℃, ensures that the heat release temperature does not damage bone tissue cells during polymerization, furthest retains the biological active ingredients of the polymethacrylic acid nitrofurfuryl alcohol ester, increases the safety of the self-curing calcium phosphate bone bonding material in use of a human body, and can effectively prevent and treat long-term implantation infection.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to bone cement, a preparation method thereof and an orthopedic implant material.
Background
The repair and treatment of bone defects is a difficult problem which afflicts surgeons for a long time, and scientists of various countries are always dedicated to the research and development of ideal bone repair materials. Bone repair materials are widely used in the fields of bone surgery, orthopedics, and dentistry. There are 3 kinds of materials classified according to sources, namely autogenous bone, allogenic bone and artificial synthetic material, although autogenous bone is an ideal bone repair material, the source of supply bone is limited and secondary operation brings pain to patients, the supply bone area may appear morphological and functional disorder; foreign bone has immunological rejection reaction, which may cause infectious diseases and tumor formation, and thus scientists in various countries have been exploring ideal bone defect repairing materials for a long time. The calcium phosphate cement is a commercially used bone grafting material, has excellent performance as a bone substitute material, and mainly shows that: good biocompatibility and biological safety, good biodegradability and guided osteogenic activity. The calcium phosphate cement can be converted into a composition similar to natural bone, can participate in metabolism after being implanted into a human body, can form bone through bone conduction, can guide the generation of new bone with the same amount while being absorbed, is beneficial to minimally invasive treatment of bone defect, but has inherent defects of the calcium phosphate cement, such as poor antibacterial performance, insufficient mechanical performance, is not beneficial to operation of doctors, and limits the application of the calcium phosphate cement in clinic.
Disclosure of Invention
The invention mainly aims to provide bone cement, a preparation method thereof and an orthopedic implant material, and aims to provide degradable bone cement with low elastic modulus and good antibacterial performance.
In order to achieve the above object, the present invention provides a bone cement, comprising:
the solid phase component comprises 80-99% of self-curing calcium phosphate cement and 1-20% of poly (nitro-furfuryl methacrylate); and (c) a second step of,
liquid phase component comprising citric acid and Na 2 HPO 4 The mixed aqueous solution of (1).
Optionally, the mass of the solid phase component per ml of the liquid phase component is (1-2) g.
Optionally, the poly (nitrofurfuryl methacrylate) comprises the following repeating units:
optionally, the structural formula of the poly (nitrofurfuryl methacrylate) is:
wherein the number average molecular weight of the poly (nitrofurfuryl methacrylate) is more than 100000.
Optionally, the self-setting calcium phosphate cement includes alpha tricalcium phosphate and dicalcium phosphate dihydrate.
The invention further provides a preparation method of the bone cement, which comprises the following steps:
s10, uniformly mixing the self-curing calcium phosphate cement and the poly (nitro furfuryl methacrylate) to obtain a solid phase component;
s20, mixing citric acid and Na 2 HPO 4 Respectively preparing into solution, mixing uniformly to obtain liquid phase component, and mixing the liquid phase component and solid phase component uniformly to obtain bone cement.
Optionally, in step S10, the temperature of the self-curing calcium phosphate cement and the poly (nitro furfuryl methacrylate) during mixing is 32-42 ℃, and the relative humidity is 40%.
Alternatively, in step S20, the mixing time of the liquid phase component and the solid phase component is 10 to 20min.
The invention further provides an orthopedic implant material, which comprises the bone cement and the stem cells inoculated in the bone cement, wherein the bone cement is the bone cement.
Optionally, the stem cells are inoculated in an amount of 2 × 10 per cubic centimeter of the bone cement 6 ～5×10 7 And (4) respectively.
According to the technical scheme, the bone cement is provided, wherein a certain proportion of the polymethyl nitryl furfuryl acrylate is added into the bone cement, the polymethyl nitryl furfuryl acrylate belongs to a bio-based material, the biological safety is high, the polymethyl nitryl furfuryl acrylate has good biological activity and excellent antibacterial performance, excellent thermal stability and mechanical performance and good bonding performance with a calcium phosphate bone bonding material, the tissue thermal injury can be effectively reduced, the heat release temperature is lower than 60 ℃, the heat release temperature is ensured not to damage bone tissue cells during polymerization, the biological active ingredients of the bone tissue cells are retained to the maximum extent, the safety of the self-curing calcium phosphate bone bonding material in use of a human body is improved, and the long-term implantation infection can be effectively prevented and treated. The bone cement provided by the invention has the advantages of low elastic modulus, good antibacterial performance and degradability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a nitrofurfuryl methacrylate monomer of an embodiment of the invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a nitrofurfuryl methacrylate monomer according to an embodiment of the invention;
FIG. 3 is a scanning electron micrograph of poly (nitrofurfuryl methacrylate) according to an embodiment of the present invention;
fig. 4 is a schematic flow chart illustrating an embodiment of a method for preparing bone cement according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if directional indications (such as up, down, left, right, front, back, outer, inner, 8230; \8230;) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative position relationship between the components, the motion condition, etc. in a specific posture (as shown in the figure), and if the specific posture is changed, the directional indications are correspondingly changed.
In addition, if there is a description of "first", "second", etc. in an embodiment of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B", including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The repair and treatment of bone defects is a difficult problem which troubles surgeons for a long time, and scientists in various countries are always dedicated to the research and development of ideal bone repair materials. Bone repair materials are widely used in the fields of bone surgery, orthopedics, and dentistry. There are 3 kinds classified according to sources, namely, autogenous bone, allogenic bone and synthetic material, although autogenous bone is an ideal bone repair material, the source of the supplied bone is limited and secondary operation brings pain to patients, and morphological and functional disorders may occur in the supplied bone region; foreign bone has immunological rejection reaction, which may cause infectious diseases and tumor formation, and thus scientists in various countries have been exploring ideal bone defect repairing materials for a long time. The calcium phosphate cement is a commercially used bone grafting material, has excellent performance as a bone substitute material, and mainly shows that: good biocompatibility and biological safety, good biodegradability and guided osteogenic activity. The calcium phosphate cement can be converted into a composition similar to natural bone, can participate in metabolism after being implanted into a human body, can form bone through bone conduction, can guide the generation of new bone with the same amount while being absorbed, is beneficial to minimally invasive treatment of bone defect, but has inherent defects of the calcium phosphate cement, such as poor antibacterial performance, insufficient mechanical performance, is not beneficial to operation of doctors, and limits the application of the calcium phosphate cement in clinic.
In view of this, the invention provides a bone cement, and aims to provide a degradable bone cement with low elastic modulus and good antibacterial performance. In the attached drawings, fig. 1 is a nuclear magnetic resonance hydrogen spectrum of a nitrofurfuryl methacrylate monomer according to an embodiment of the invention; FIG. 2 is a nuclear magnetic resonance carbon spectrum of a nitrofurfuryl methacrylate monomer according to an embodiment of the present invention; FIG. 3 is a scanning electron micrograph of poly (nitrofurfuryl methacrylate) according to an embodiment of the invention; fig. 4 is a schematic flow chart illustrating an embodiment of a method for preparing bone cement according to the present invention.
The invention provides a bone cement, which comprises:
the solid phase component comprises 80-99% of self-curing calcium phosphate cement and 1-20% of poly (nitro-furfuryl methacrylate); and the number of the first and second groups,
liquid phase component comprising citric acid and Na 2 HPO 4 The mixed aqueous solution of (1).
According to the technical scheme, the bone cement is provided, wherein a certain proportion of the polymethyl nitryl furfuryl acrylate is added into the bone cement, the polymethyl nitryl furfuryl acrylate belongs to a bio-based material, the biological safety is high, the polymethyl nitryl furfuryl acrylate has good biological activity and excellent antibacterial performance, excellent thermal stability and mechanical performance and good bonding performance with a calcium phosphate bone bonding material, the tissue thermal injury can be effectively reduced, the heat release temperature is lower than 60 ℃, the heat release temperature is ensured not to damage bone tissue cells during polymerization, the biological active ingredients of the bone tissue cells are retained to the maximum extent, the safety of the self-curing calcium phosphate bone bonding material in use of a human body is improved, and the long-term implantation infection can be effectively prevented and treated. The bone cement provided by the invention has the advantages of low elastic modulus, good antibacterial performance and degradability.
The invention is not limited with regard to the proportion of the solid-phase component and the liquid-phase component, and preferably, the mass of the solid-phase component per milliliter of the liquid-phase component is (1-2) g. The bone cement has low elastic modulus, good antibacterial property and easy degradation.
The invention also does not limit the specific structural formula of the nitro furfuryl methacrylate, and preferably, the nitro furfuryl methacrylate comprises the following repeating units:
experiments show that the polymer with the repeating units is adopted, so that the bone cement is low in elastic modulus, good in antibacterial performance and easier to degrade.
Further, the structural formula of the poly (nitro-furfuryl methacrylate) is as follows:
Wherein the number average molecular weight of the poly nitro furfuryl methacrylate is more than 100000.
FIG. 1 shows the NMR spectrum of a nitro furfuryl methacrylate monomer used in the example of the present invention: ( 1 H-NMR), and (c) in the presence of a hydrogen peroxide, FIG. 2 shows the nuclear magnetic carbon spectrum of nitrofurfuryl methacrylate used in the example of the invention (C) 13 C-NMR), fig. 3 is a scanning electron microscope image of the poly (nitrofurfuryl methacrylate) formed by polymerizing the nitrofurfuryl methacrylate monomer, which is adopted in the embodiment of the present invention, and it can be known that the poly (nitrofurfuryl methacrylate) is substantially uniform and spherical, and the poly (nitrofurfuryl methacrylate) adopting the structural formula and the molecular weight has the advantages of excellent bone cement antibacterial performance, high biocompatibility, degradable bio-based composite bone cement, high strength, good toughness, strong plasticity, and fast curing.
The invention also does not limit the type of the self-curing calcium phosphate cement, preferably, the self-curing calcium phosphate cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate, and experiments show that the antibacterial performance of the bone cement can be further enhanced by adopting the two types of the self-curing calcium phosphate cement and the calcium hydrophosphate dihydrate.
In the case of the liquid phase component, citric acid and Na 2 HPO 4 The invention is not limited, preferably, in the embodiment of the invention, the citric acid solution with the mass fraction of 5% and the Na with the concentration of 0.5mol/L are added 2 HPO 4 Mixing the solutions to obtain liquid phase component, citric acid and Na 2 HPO 4 The volume ratio of (2-4): 1, the liquid phase components in the proportion are adopted, so that the obtained bone cement is low in elastic modulus, good in antibacterial performance and easier to degrade.
Referring to fig. 4, the present invention further provides a method for preparing the bone cement, comprising the following steps:
s10, uniformly mixing the self-curing calcium phosphate cement and the poly (nitro furfuryl methacrylate) to obtain a solid phase component;
preferably, in this step, the temperature of the operation is 32 to 42 ℃ and the relative humidity is 40%, and under the above operation conditions, the obtained powder is more uniform and stable.
S20, mixing citric acid and Na 2 HPO 4 Respectively preparing into solution, uniformly mixing to obtain liquid phase component, and uniformly mixing the liquid phase component and the solid phase component to obtain the bone cement.
After mixing the solid-phase component and the liquid-phase component, preferably, it is left to stand for 3 to 10min to allow the solid-phase component and the liquid-phase component to be sufficiently contacted, and then mixed.
Preferably, in step S20, the mixing time of the liquid phase component and the solid phase component is 10 to 20min. In the embodiment of the invention, the liquid phase component also plays a role of an initiator, and after the liquid phase component and the solid phase component are mixed, the solid phase component simultaneously carries out the cross-linking reaction of the poly (nitrofurfuryl methacrylate) and the curing reaction of the self-curing calcium phosphate cement to form the cement.
The preparation method of the bone cement provided by the invention is simple, convenient to operate and low in cost, has all the beneficial effects of the bone cement, and is not repeated herein.
An example of the method for preparing the bone cement according to the present invention is given below:
(1) Uniformly mixing self-curing calcium phosphate bone cement and polymethyl methacrylate nitro furfuryl alcohol ester to obtain a solid phase component, wherein the polymethyl methacrylate nitro furfuryl alcohol ester is A, the molecular weight is more than 100000, the self-curing calcium phosphate bone cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate, the mass fraction of the self-curing calcium phosphate bone cement in the solid phase component is 80-99%, the mass fraction of the polymethyl methacrylate nitro furfuryl alcohol ester is 1-20%, and the mass of the solid phase component corresponding to each milliliter of the liquid phase component is (1-2) g;
(2) At a temperature of 32-42 ℃ and a phaseUnder the condition of 40% of humidity, adding a citric acid solution with the mass fraction of 5% and Na with the concentration of 0.5mol/L 2 HPO 4 Mixing the solutions to obtain liquid phase component, citric acid and Na 2 HPO 4 The volume ratio of (2-4): 1, mixing the liquid phase component and the solid phase component for 10-20 min to obtain the bone cement.
The invention further provides an orthopedic implant material, which comprises bone cement and stem cells inoculated on the bone cement, wherein the bone cement is the bone cement. The orthopedic implant material provided by the invention comprises the bone cement, at least has all the beneficial effects of the bone cement, and is not repeated herein.
Preferably, the amount of stem cells inoculated per cubic centimeter of the bone cement is 2 x 10 6 ～5×10 7 And (4) respectively. Within the range of the inoculation amount, the orthopedic implant material has good repairing and treating effects.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
(1) Uniformly mixing 18g of self-curing calcium phosphate bone cement and 2g of poly (nitrofurfuryl methacrylate) to obtain a solid phase component, wherein the poly (nitrofurfuryl methacrylate) is A, the molecular weight is more than 100000, the self-curing calcium phosphate bone cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate, and in the solid phase component, the mass fraction of the self-curing calcium phosphate bone cement is 90% and the mass fraction of the poly (nitrofurfuryl methacrylate) is 10%;
(2) Under the conditions of 35 ℃ and 40% relative humidity, 8mL of citric acid solution with the mass fraction of 5% and 2mL of Na with the concentration of 0.5mol/L 2 HPO 4 And mixing the solution to obtain a liquid phase component, and mixing the liquid phase component and a solid phase component for 20min to obtain the bone cement, wherein the mass of the solid phase component corresponding to each milliliter of the liquid phase component is 2g.
Example 2
(1) Uniformly mixing 14.4g of self-curing calcium phosphate bone cement and 3.6g of poly (nitro furfuryl methacrylate) to obtain a solid phase component, wherein the poly (nitro furfuryl methacrylate) is A, the molecular weight is more than 100000, the self-curing calcium phosphate bone cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate, and in the solid phase component, the mass fraction of the self-curing calcium phosphate bone cement is 80% and the mass fraction of the poly (nitro furfuryl methacrylate) is 20%;
(2) Under the conditions of 42 ℃ of temperature and 40 percent of relative humidity, 7.65mL of citric acid solution with the mass fraction of 5 percent and 2.35mL of Na with the concentration of 0.5mol/L 2 HPO 4 And (3) mixing the solution, namely mixing the liquid phase component and the solid phase component for 10min to obtain the bone cement, wherein the mass of the solid phase component corresponding to each milliliter of the liquid phase component is 1.8g.
Example 3
(1) Uniformly mixing 14.85g of self-curing calcium phosphate bone cement and 0.15g of poly (nitro furfuryl methacrylate) to obtain a solid phase component, wherein the poly (nitro furfuryl methacrylate) ester is A, the molecular weight is more than 100000, the self-curing calcium phosphate bone cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate, and in the solid phase component, the mass fraction of the self-curing calcium phosphate bone cement is 99% and the mass fraction of the poly (nitro furfuryl methacrylate) ester is 1%;
(2) Under the conditions of 32 ℃ and 40% of relative humidity, 6.67mL of citric acid solution with the mass fraction of 5% and 3.33mL of Na with the concentration of 0.5mol/L 2 HPO 4 And mixing the solution to obtain a liquid phase component, and mixing the liquid phase component and a solid phase component for 15min to obtain the bone cement, wherein the mass of the solid phase component corresponding to each milliliter of the liquid phase component is 1.5g.
Example 4
(1) Uniformly mixing 17g of self-curing calcium phosphate bone cement and 3g of poly (nitro-furfuryl methacrylate) to obtain a solid phase component, wherein the poly (nitro-furfuryl methacrylate) is A, the molecular weight is more than 100000, the self-curing calcium phosphate bone cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate, and in the solid phase component, the mass fraction of the self-curing calcium phosphate bone cement is 85 percent, and the mass fraction of the poly (nitro-furfuryl methacrylate) is 15 percent;
(2) Under the conditions of 35 ℃ and 40% relative humidity, 8mL of citric acid solution with the mass fraction of 5% and 2mL of 0.5 mol/mL-Na of L 2 HPO 4 And mixing the solution to obtain a liquid phase component, and mixing the liquid phase component and a solid phase component for 20min to obtain the bone cement, wherein the mass of the solid phase component corresponding to each milliliter of the liquid phase component is 1g.
Comparative example 1
The components and preparation method are the same as example 1 except that the solid phase component includes only the self-setting calcium phosphate cement.
The final setting time, compressive strength, elastic modulus, sterilization rate of Escherichia coli, sterilization rate of Staphylococcus aureus, and adverse reactions of the bone cements of each example and comparative example were measured according to ISO standard 5833 and ISO standard 16886, and Table 1 was obtained.
TABLE 1 determination of the Properties of the bone cements of the examples and comparative examples
As can be seen from Table 1, the cement of comparative example 1, in which no nitrofurfuryl methacrylate was added, had a final set time of 34.6min, whereas the cement of examples 1 to 4, in which nitrofurfuryl methacrylate was added, had a significant reduction in the final set time. In particular, in the embodiment 3, the final setting time is 10.6min, so that the setting time of the calcium phosphate bone cement is greatly shortened, the problem that the setting time is too long in clinical use of the medical bonding material for orthopedics department is solved, and the safety of the calcium phosphate bone bonding material in use of a human body is improved; the mechanical strength of the medical composite adhesive material for orthopedics department added with the polymethyl nitrofurfuryl methacrylate is not reduced, the elastic modulus is reduced, and the hidden danger of secondary fracture caused by uneven bone stress conduction in vivo due to overhigh strength of a single self-curing calcium phosphate bone adhesive material is avoided; finally, an antibacterial experiment shows that the orthopedic medical composite adhesive material added with the polymethyl methacrylate nitrofurfuryl alcohol ester has excellent antibacterial performance and can effectively prevent and treat the problem of long-term implantation infection.
In conclusion, the bone cement provided by the invention is added with the poly (nitrofurfuryl methacrylate) in a certain proportion, the poly (nitrofurfuryl methacrylate) belongs to a bio-based material, has high biological safety, better biological activity and excellent antibacterial property, excellent thermal stability and mechanical property, good binding property with a calcium phosphate bone bonding material, can effectively reduce tissue thermal injury, has the heat release temperature lower than 60 ℃, ensures that the heat release temperature does not damage bone tissue cells during polymerization, furthest retains the bioactive components of the bone cement, increases the safety of the self-curing calcium phosphate bone bonding material in use of a human body, and can effectively prevent and treat long-term implantation infection.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (6)
1. A bone cement, comprising:
the solid phase component comprises 80 to 99 mass percent of self-curing calcium phosphate cement and 1 to 20 mass percent of poly (nitro-furfuryl methacrylate); and the number of the first and second groups,
liquid phase component comprising citric acid and Na 2 HPO 4 The mixed aqueous solution of (1); wherein,
the mass of the solid phase component corresponding to each milliliter of the liquid phase component is (1-2) g;
the poly nitro furfuryl methacrylate comprises the following repeating units:
the structural formula of the poly (nitro-furfuryl methacrylate) is as follows:
the number average molecular weight of the poly nitro furfuryl methacrylate is more than 100000;
the self-curing calcium phosphate cement comprises alpha-tricalcium phosphate and calcium hydrophosphate dihydrate.
2. A method of preparing a bone cement according to claim 1, comprising the steps of:
s10, uniformly mixing the self-curing calcium phosphate cement and the poly (nitro furfuryl methacrylate) to obtain a solid phase component;
s20, mixing citric acid and Na 2 HPO 4 Respectively preparing into solution, mixing uniformly to obtain liquid phase component, and mixing the liquid phase component and solid phase component uniformly to obtain bone cement.
3. The method for preparing a bone cement according to claim 2, wherein the temperature at which the self-setting calcium phosphate bone cement and the polynitrofurfuryl methacrylate are mixed is 32 to 42 ℃ and the relative humidity is 40% in step S10.
4. The method for preparing bone cement according to claim 2, wherein the mixing time of the liquid phase component and the solid phase component is 10-20 min in step S20.
5. An orthopedic implant material comprising a bone cement according to claim 1 and stem cells seeded on said bone cement.
6. The orthopedic implant material of claim 5, wherein said stem cells are inoculated in an amount of 2 x 10 per cubic centimeter of said bone cement 6 ～5×10 7 And (4) respectively.
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| JPS5788106A (en) * | 1980-11-19 | 1982-06-01 | Hidekazu Masuhara | Fluorine ion prolongably releasing material and dental material using it |
| JP2548745B2 (en) * | 1987-10-15 | 1996-10-30 | 住友大阪セメント株式会社 | Bone cement composition |
| JP2751938B2 (en) * | 1989-10-19 | 1998-05-18 | 宣男 中林 | Bone cement composition and hardened body |
| CA2027921C (en) * | 1989-10-19 | 1997-12-09 | Nobuo Nakabayashi | Bone cement composition, cured product thereof, implant material and process for the preparation of the same |
| US5149368A (en) * | 1991-01-10 | 1992-09-22 | Liu Sung Tsuen | Resorbable bioactive calcium phosphate cement |
| GB0514076D0 (en) * | 2005-07-08 | 2005-08-17 | Depuy Int Ltd | Bioactive bone cement composition |
| CN101057979B (en) * | 2007-04-03 | 2010-06-09 | 暨南大学 | Injectable self-curable calcium phosphate bone tissue repairing material and its preparation method and application |
| PT2022446E (en) * | 2007-07-30 | 2012-07-04 | Purzer Pharmaceutical Co Ltd | Bio-degenerable bone cement and manufacturing method thereof |
| CN102688522A (en) * | 2011-03-21 | 2012-09-26 | 上海睿平生物技术有限公司 | Novel mixed bone cement |
| CN103961741A (en) * | 2014-05-14 | 2014-08-06 | 常州大学 | Calcium phosphate bone repair material and preparation method thereof |
| JP6424532B2 (en) * | 2014-09-17 | 2018-11-21 | 東洋インキＳｃホールディングス株式会社 | Method for producing furfuryl methacrylate |
| CN106620841B (en) * | 2016-12-22 | 2019-09-03 | 宁波华科润生物科技有限公司 | Low temperature injectable acrylic resin bone cement and preparation method thereof |
| CN107412852A (en) * | 2017-07-26 | 2017-12-01 | 山东冠龙医疗用品有限公司 | Bone cement compositions and its set group |
| DE102017123009A1 (en) * | 2017-10-04 | 2019-04-04 | Kulzer Gmbh | Dental composite material and milling blanks of this composite material |
| CN108273131B (en) * | 2018-03-19 | 2021-07-27 | 深圳市中科海世御生物科技有限公司 | Composite bone cement, preparation method and application thereof, and bone repair material |
| CN112245657B (en) * | 2020-10-19 | 2022-07-01 | 合肥中科智远生物科技有限公司 | Low-heat-release antibacterial bone cement and preparation method and application thereof |
| CN112245649B (en) * | 2020-10-19 | 2022-01-28 | 合肥中科智远生物科技有限公司 | Orthopedic composite adhesive material and preparation method thereof |
| CN113491790A (en) * | 2021-07-19 | 2021-10-12 | 中国科学技术大学 | Antibacterial bone cement and preparation method and application thereof |
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